Water-insoluble poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers for defoaming aqueous media

ABSTRACT

The invention relates to the use of water-insoluble poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers of the general average formula                    
     wherein the variables are described herein as defoaming agents for aqueous media. This invention also provides for defoaming compositions comprising said water-insoluble poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers.

RELATED APPLICATIONS

The application is a divisional of application U.S. Ser. No. 09/569,743, filed on May 11, 2000, now U.S. Pat. No. 6,451,863, and claims priority to German application No. 199 22 218.5, filed May 14, 1999. These applications are both herein incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to the use of water-insoluble poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers for defoaming aqueous media.

In numerous industrial processes, aqueous formulations use surface-active substances in order, for example, to emulsify water-insoluble substances or to reduce the interfacial tension and so achieve better wetting characteristics. An unwanted accompanying effect of these surface-active substances, however, is that air introduced during the preparation and processing of such water-based formulations is stabilized as foam. Examples of processes in which such problems occur include papermaking, wastewater treatment, emulsion polymerization, and the manufacture and application of water-dilutable coating systems.

Foam of this kind, produced in the course of stirring or dispersing operations during manufacture or filling, prolongs production times and reduces the effective capacity of the production plant. Foam is disruptive to the application of coating materials since it leads to unwanted surface defects. As a result, the use of antifoams or defoamers in virtually all water-based systems is widespread and often indispensable.

In the past, a large number of formulations have been described which envisage the use of, for example, silicone oils, organomodified siloxanes, hydrophobic polyoxyalkylenes, mineral oils, natural oils and other hydrophobic liquids as defoaming substances. Frequently, the above-mentioned substances are used in combinations with hydrophobic solids, such as pyrogenic silicas, metal stearates or fatty acid amides, for example, which often intensify the foam inhibiting or defoaming effect.

In accordance with the present state of knowledge, it is critical to the defoaming action of a defoamer that it is able to penetrate into the foam lamellae and to weaken them until they collapse. To achieve this requires a controlled incompatibility (hydrophobicity) with the aqueous phase to be defoamed: if a defoamer is too compatible (hydrophilic), it will not be able to be very effective since it does not penetrate preferentially into the foam lamella. If the degree of incompatibility is too great, then defoaming is generally very good but there are frequently the unwanted side effects of surface defects, deterioration in wetting characteristics, and separation phenomena.

Consequently, the search for a suitable defoamer is always a search for the correct incompatibility/compatibility balance for the system to be defoamed, with the aim of getting as close as possible to the target hydrophobicity/hydrophilicity equilibrium.

2. Description of the Related Art

In the past, polyoxyalkylene-polysiloxane block copolymers have proven suitable for allowing this equilibrium to be established in a particularly variable manner, as is described, inter alia, in U.S. Pat No. 3,763,021.

When polyoxyalkylene-polysiloxane block copolymers are used, advantage is taken of the fact that the polysiloxane blocks can be modified in a targeted manner with polyoxyalkylene units which, by virtue of their composition from hydrophilic and hydrophobic polyoxyalkylene units, can be adapted, in interplay with the polysiloxane block, to the abovementioned desired hydrophobicity/hydrophilicity equilibrium.

The prior art, an example of which that may be mentioned here is DE-C-1 012 602, includes polyoxyalkylene-polysiloxane block copolymers in which the polyoxyalkylene block is defined as (C_(n)H_(2n)O)_(x). The index n is an integer from 2 to 4, it being essential that these polyoxyalkylene blocks always include —CH₂—CHR—O— groups as a common structural element, R being a hydrogen atom, a methyl group or an ethyl group. Such polyoxyalkylene blocks are prepared by ionic addition polymerization of oxirane derivatives, such as ethylene oxide, propylene oxide and butylene oxide. The basic structure of the properties-determining polyoxyalkylene chain is always, however, the continually repeating sequence of the two carbon atoms and one oxygen atom along the polyoxy-alkylene chain. Nor is this principle altered by the use of epoxides of longer-chain olefins.

Typically, however, polyoxyethylenes and polyoxy-propylenes are used in the polyoxyalkylene-polysiloxane block copolymers of the prior art.

By varying the oxyalkylene units, and in particular by modifying their respective proportions and their sequence in the polymer (random and/or in blocks), a large number of polyoxyalkylene-polysiloxane block copolymers are obtainable.

Because of the restriction to these basic units described above, however, in many cases it has not been possible to date to find the optimum incompatibility/compatibility balance required for certain defoamers.

OBJECT OF THE INVENTION

Therefore, an object of the present invention to provide particularly suitable polyoxyalkylene-polysiloxane block copolymers for defoaming aqueous media, said copolymers making it possible to establish the above-described desired incompatibility/compatibility balance in a targeted manner better than as has been possible to date.

SUMMARY OF THE INVENTION

Surprisingly, this object is achieved by the use of water-insoluble poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers of the general average formula I:

where

R¹ and/or R⁷ are R² or —[R⁴]_(w)—[R⁵]_(x)—[R⁶]—R⁸,

R² and R³ are identical or different alkyl radicals, preferably having 1 to 24 carbon atoms, or are unsubstituted or substituted aryl radicals, preferably having up to 24 carbon atoms, with phenyl being especially preferred.

R⁴ is a divalent radical of the formula —O—, —NH—, —NR²—, —S— or of the formula

 —[O—Si(CH₃)₂]_(u—)

where

 u is from 2 to 200,

R⁵ is identical or different alkylene radicals, preferably having-1 to 24 carbon atoms, or is

—C_(n)H_(2n-f)R² _(l)—O—C_(m)H_(2m-g)R² _(g)—

 where

f is from 0 to 12,

g is from 0 to 12,

n is from 1 to 18,

m is from 1 to 18,

R⁶ is identical or different radicals of the general formula

—O—(C₂H_(4-a)R⁹ _(a)O)_(b)(CH₂—CH₂—CH₂—CH_(2-c)R¹⁰ _(c)O)_(d—)

 where

R⁹ is identical or different alkyl radicals, preferably having 1 to 4 carbon atoms.

R¹⁰ is an alkyl radical, preferably having 1 to 6 carbon atoms,

but where, taking into account all radicals R⁶, the proportion of C₂H₄O groups

among the total of all radicals R⁶ does not exceed 40% by weight,

a is from 0 to 3,

b is from 0 to 200,

c is from 0 to 2,

d is from 2 to 40,

the sum (b+d)=3 to 240

and the sequence of the individual polyoxyalkylene segments —(C₂H_(4-a)R⁹ _(a)O)_(b)— and —(CH₂—CH₂—CH₂—CH_(2-c)R¹⁰ _(c)O)_(d)— can be as desired and, in particular, embraces block copolymers, such as random polymers and combinations thereof,

R⁸ is a hydrogen, a substituted or unsubstituted alkyl radical, preferably having from 1 to 6 carbon atoms, or an acyl radical,

v is from 3 to 200,

w is from 0 or 1,

x is from 0 or 1,

y is from 0 to 200,

and, if y=0, R¹ and/or

R⁷ are/is —[R⁴]_(w)—[R⁵]_(x)—[R⁶]—R⁸.

DETAILED DESCRIPTION OF THE INVENTION

In many cases, polyoxyalkylene-polysiloxane block copolymers, which have proven highly suitable, are those obtained by means of combinations of two polyoxyalkylene units with one or more polysiloxane copolymers. In that case, the distinction in the case of the polyoxyalkylene copolymers can be a distinction in relation either to the relative proportion of the units used for the preparation of this copolymer or to the molecular weight of the whole polyoxyalkylene unit, or else can lie in its functionality.

Different polysiloxane copolymers can be distinguished in accordance with both their molecular mass and their degree of branching or the number and/or relative position of the reactive groups used which are available for linkage.

The mode of action of the compounds of the invention is expressly not that they bring about particularly good compatibilization between constituents of a mixture that differ in polarity. Rather, it is the case that they themselves are just compatible enough not to induce any unwanted side effects such as surface defects, deteriorations in the wetting characteristics, or separation phenomena, without bringing about the compatibilization of other constituents.

A decisive factor in comparison with the prior art is that the compounds of the invention deviate from the above-described “standard construction principle” of the —CH₂—CHR—O— groups and instead contain —CH₂—CH₂—CH₂—CH₂—O— groups, which also have a particularly positive effect on the incompatibility/compatibility balance which is essential for effective defoaming without unwanted side effects.

Such poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers can be prepared in accordance with customary methods as in the prior art. As the skilled worker is well aware, such methods include, in particular, the hydrosilylation reaction of additionally olefinically unsaturated poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers with hydropolysiloxanes or the nucleophilic substitution of poly(oxy-1,4-butanedyiy)-containing polyoxyalkylene-polysiloxane block copolymers with nucleophilic groups on polysiloxanes containing at least one silicon atom substituted by an electronegative group. Processes of this kind and the preparation of appropriate polysiloxanes are described, for example, in W. Noll “Chemie undechnologie der Silicone”, Verlag Chemie, Weinheim, 1968.

In accordance with the prior art, the poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers required for this purpose can be obtained by ionic polymerization of tetrahydrofuran and its derivatives and of appropriately substituted oxiran derivatives.

An important feature of the present invention that the poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers of the invention are not water-soluble at the customary processing temperature of the media to be defoamed. This means that a 1:1 mixture (% by weight) with water leads to a nonhomogeneous mixture of the two phases and that no dissolving of the poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers of the invention takes place. However, small fractions of free polyoxyalkylenes may be present in the poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers as a result of their preparation, as set out below. Since the preparation of these copolymers essentially obeys the laws of statistics, it is also possible for particularly oxyethylene-rich polyoxyalkylenes to occur, which in turn may be soluble in water. These fractions, however are very small and in the poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers of the invention are always less than 10% by weight.

EXAMPLES

In order to illustrate the claimed compounds, the following polytiloxanes 1 to 3 were reacted, by way of example, with the polyoxyalkylenes 1 to 6:

TABLE 1 Polysiloxane 1 (CH₃)₃SiO—[(CH₃)₂SiO—]₂₀[(CH₃)HSiO—]₅ Si(CH₃)₃ Polysiloxane 2 (CH₃)₂HSiO—[(CH₃)₂SiO—]₃₀[(CH₃)HSiO—]₄ SiH(CH₃)₂ Polysiloxane 3 (CH₃)₂ClSiO—[(CH₃)₂SiO—]₁₃SiCl(CH₃)₂ Polyoxyalkylene 1 H₂C═CH—CH₂O—(C₂H₄O—)₆(CH₂CH(CH₃) O—)₁₈H Polyoxyalkylene 2 H₂C═CH—CH₂O—(C₂H₄O—)₁₈(C₄H₈O—)₃H Polyoxyalkylene 3 H₂C═CH—CH₂O—(C₂H₄O—)₆(C₄H₈O—)₁₄H Polyoxyalkylene 4 H₃C—CH₂—CH₂—CH₂O—(C₂H₄O—)₆(CH₂ CH(CH₃)O—)₁₈H Polyoxyalkylene 5 H₃C—CH₂—CH₂—CH₂O—(C₂H₄O—)₁₈ (C₄H₈O—)₃H Polyoxyalkylene 6 H₃C—CH₂—CH₂—CH₂O—(C₂H₄O—)₆ (C₄H₈O—)₁₄H

The skilled worker is well aware that the compounds are obtained in the form of mixtures of their homologes and that the indices stated denote average values.

In accordance with the table below, the following polyoxyalkylene-polysiloxane block copolymers are obtained.

TABLE 2 Polyoxyalkylene Inventive Example Siloxane (val %) (val %) yes/no 1 1 1(100) — no 2 1 2(100) — no 3 1 3(100) — yes 4 2 1(100) — no 5 2 2(100) — no 6 2 3(100) — yes 7 3 4(100) — no 8 3 5(100) — no 9 3 6(100) — yes 10 3 4(50) 6(50) yes

Examples 1 to 6 were prepared in accordance with processes customary from the literature, as described, for example, in DE-B-11 65 028; examples 7 to 10 were prepared in accordance with processes customary from the literature, as described, for example, in U.S. Pat. No. 2,846,458.

The skilled worker is well aware that with this mode of preparation, corresponding to the prior art, it is possible for free polyoxyalkylene still to be present in the polyoxyalkylene-polysiloxane block copolymers. As a general rule, this is not disruptive and need not be removed for the subsequent use of the compounds.

For use as defoamers, the water-insoluble poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers of the invention are advantageously formulated as follows:

a) 72 to 85% by weight of the poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers,

b) from 15 to 28% by weight of a nonionic ethoxylate having a HLB of from 8 to 12, and

c) from 0.1 to 10% by weight, based on the sum a)+b), of an organic or inorganic solid substance.

Examples of nonionic ethoxylates having a HLB (hydrophilic/lipophilic balance; definition as per W. C. Griffin; J. Soc. Cosmet. Chem., Volume 5, page 249, 1954) of 8-12 are fatty acid esters of polyvalent alcohols, the polyethylene glycol derivatives thereof, polyglycol derivatives of fatty acids and fatty alcohols, alkylphenol ethoxylates, and block copolymers of ethylene oxide and propylene oxide (Pluronics). Preference is given to ethoxylates of raw materials obtainable from naturally occurring fats, especially oleyl derivatives and stearyl derivatives.

Examples of the organic or inorganic solid substances are silicas, alumina, alkaline earth metal carbonates, alkaline earth metal salts of long chain fatty acids, the amides thereof, and urea derivatives. These substances may also have been additionally hydrophobicized in accordance with known methods.

The formulated defoamers described above can be used as they are or in the form of their aqueous emulsion. Emulsions are frequently used with preference since they are easier to meter. Particular preference is given to defoamer emulsions whose average particle diameter lies between 1 and 10 μm. Such emulsions then contain between 5 and 50% by weight of the poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers of the invention.

Performance testing takes place in emulsion paints to which defoamer is added conventionally in amounts of from 0.01 to 0.5% by weight based on the emulsion paint.

The following formulations were prepared and tested:

TABLE 3 Polyoxyalkylene-polysiloxane Inventive Formulation block copolymer from example yes/no 1 1 no 2 2 no 3 3 yes 4 4 no 5 5 no 6 6 yes 7 7 no 8 8 no 9 9 yes 10 10 yes

The compositions of formulations 1 to 10 are as follows:

75% by weight polyoxyalkylene-polysiloxane block copolymer as per Example 1 to 9

20% by weight oleyl ethoxylate with a HLB of 10

5% by weight silica.

Testing was carried out in the following emulsion paints:

Emulsion paint 1 (all amounts in % by weight) Propylene glycol 4.7 Collacral ® AS 35 5.0 BASF (polyacryalate dispersing agent) Titanium dioxide 23.1 Mergal ® K7 0.2 Riedel de Haen (formaldehyde-free preservative) Butyl glycol 2.6 Dowanol ® DPM 1.3 Dow (dipropylene glycol methyl ether) Water 6.8 Acronal ® A603 52.3 BASF (acrylate dispersion) Rheolate ® 278 4.0 Rheox (polyurethane-based thickner) Emulsion paint 2 (all amounts in % by weight) Water 36.4 Coatex ® P50 0.4 Coatex (polyurethane-based thickner) Calgon ® N 0.1 BK Ladenburg (sodium polyphosphate) Mergal ® K7 0.2 Riedel de Haen (formaldehyde-free preservative) Coatex ® BR100 2.3 Coatex (polyurethane-based thickener)

Calcidar ® Extra 22.1 Omya (calcium carbonate) Titanium dioxide 17.5 Finntalc ® M15 4.7 Finnchemicals (talcum) NaOH, 10% 0.1 Acronal ® 290D 16.2 BASF (Styrene acrylate dispersion)

The emulsion paints were formulated in accordance with the prior art. All raw materials were used without further purification. To end, 0.06% by weight of defoamer (formulation 1 to 9) was added and was incorporated by stirring at 1000 rpm for 1 minute.

A so-called roller test was carried out, the result of which is shown in the Tables below. The roller test firstly allows comparison to be made under conditions close to those in practice and secondly offers the possibility of reasonable differentiation of different formulations.

For the roller test, 40 grams of the test emulsion paint are spread using an open-pored foam roller onto a nonabsorbent test card having a total surface area of 500 cm². Prior to the application of the paint, the foam roller is wetted with water. It must be ensured that the additional amount of water introduced into the applied paint is always the same, so that the drying time of the paint always remains the same. The wet film addon is approximately 300 g/m². After 24 hours of drying time, the test cards are examined in accordance with the following criteria:

a) Macrofoam (number of bubbles per 100 cm²)

b) Microfoam (number of pinholes in comparison to photos of reference cards on a scale of 1 (very few or no pinholes) to 5 (very large number of pinholes))

c) Wetting defects (none, slight, severe)

The tests were repeated with emulsion paints which had been admixed with defoamer and kept at 50° C. for 6 weeks.

Results for Emulsion Paint 1:

TABLE 4 Macrofoam For- im- Microfoam Wetting defects mulation mediate 6 weeks immediate 6 weeks immediate 6 weeks none 80 80 5 5 none none 1 1 3 1 2 none slight 2 71 86 3 3 slight slight 3 0 1 1 1 none none 4 2 6 1 2 none slight 5 56 65 2 3 severe severe 6 0 0 1 1 none none 7 1 8 1 2 slight slight 8 27 31 2 2 slight severe 9 0 0 1 1 none none 10 0 1 0 1 none none

TABLE 5 Macrofoam For- im- Microfoam Wetting defects mulation mediate 6 weeks immediate 6 weeks immediate 6 weeks None 50 50 4 4 none none 1 1 6 1 2 none slight 2 58 61 3 3 none slight 3 0 3 1 1 none none 4 2 10 1 2 none slight 5 39 45 2 3 severe severe 6 0 1 1 1 none none 7 3 9 2 2 slight slight 8 19 25 1 2 slight severe 9 0 0 1 1 none none 10 0 0 0 1 none none

It is found that the poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymers of the invention, which are present in the formulations 3, 6, 9 and 10, offer outstanding possibilities for adapting the properties to the requirements of defoaming aqueous media Surprisingly, it is possible to achieve particular effects which are not possible even with comparably insoluble polyoxyalkylene-polysiloxane block copolymers based on substituted or unsubstituted oxirane derivatives.

the above description is intended to be illustrative and not limiting. Various changes and modifications in the embodiments described herein may occur to those skilled in the art. Those changes can be made without departing from the scope or the invention. 

What is claimed is:
 1. A defoaming composition which comprises a water-insoluble poly(oxy-1,4-butanediyl)-containing polyoxyalkylene-polysiloxane block copolymer of the average general formula

where R¹ and/or R⁷ are R² or —[R⁴]_(w)—[R⁵]_(x)—R⁶—R⁸, R² and R³ are identical or different alkyl radicals or are unsubstituted or substituted aryl radicals, R⁴ is a divalent radical of the formula —O—, —NH—, —NR²—, —S— or of the formula —[O—Si(CH₃)₂]_(u)—,  where u is from 2 to 200, R⁵ is identical or different alkylene radicals having 1 to 24 carbon atoms, or is —C_(n)H_(2n-f)R² _(f)—O—C_(m)H_(2m-g)R² _(g)—,  where, f is from 0 to 12, g is from 0 to 12, n is from 1 to 18, m is from 1 to 18, R⁶ is identical or different radicals of the general formula —O—(C₂H_(4-a)R⁹ _(a)O)_(b)(CH₂—CH₂—CH₂—CH_(2-c)R¹⁰ _(c)O)_(d)—  where, R⁹ is identical or different alkyl radicals, R¹⁰ is an alkyl radical, but where, taking into account all radicals R⁶, the proportion of C₂H₄O groups among the total of all radicals R⁶ does not exceed 40% by weight, a is from 0 to 3, b is from 0 to 200, c is from 0 to 2, d is from 2 to 40, the sum (b+d)=3 to 240 and the sequence of the individual polyoxyalkylene segments —(C₂H_(4-a)R⁹ _(a)O)_(b)— and —(CH₂—CH₂—CH₂—CH_(2-c)R¹⁰ _(c)O)_(d)— and is either random or block or combinations thereof, R⁸ is a hydrogen, a substituted or unsubstituted alkyl radical, or an acyl radical, v is from 3 to 200, w is 0 or 1, x is 0 or 1, y is from 0 to 200, and, if y is 0, R¹ and/or R⁷ are/is —[R⁴]_(w)—[R⁵]_(x)—R⁶—R⁸; a nonionic ethoxylate having an HBL from 8 to 11 and, optionally, a solid whereby said polysiloxane block copolymer is greater than 90% by weight of all polysiloxane block copolymers in the defoaming composition.
 2. A defoaming composition according to claim 1, which is an aqueous emulsion.
 3. A cooling lubricant which comprises a defoaming composition according to claim
 1. 4. A polymer dispersion which comprises a defoaming composition according to claim
 1. 5. A coating composition or printing ink which comprises a defoaming composition according to claim
 1. 